Surfactants, Micelles,

Emulsions
 Surfactants
Surface active agents
Amphiphiles
Detergents
Tensides
In most cases, solvent is water
hydrophilic (polar) group (head group)
hydrophobic alkyl chains (tail group)
 Surfactants
anionic
cationic
nonionic
amphoteric (zwitterionic)
 Anionic Surfactants
head group negatively charged
e.g. carboxylate, sulfonate, sulfate
most commonly used surfactants
example SDS (C12H25OSO3Na)
 Cationic Surfactants
Headgroup positively charged
not so common (low biodegradability)
example: DTAB C12H25N(CH3)3Br
 Nonionic Surfactants
Uncharged, but polar headgroup
second most common used surfactants
example: Alkylethylene oxides as e.g.
C10H21(OCH2CH2)8OH, also writen as
C10E8
 Amphoteric Surfactants
Headgroup contains both positive and
negative charge
seldom used (more expensive)
examples: mainly lipids
Surfactants
Surfactants
Micelles
Structure of Surfactants in Solution

Micelles
Cylinders
Bilayers
Critical Micellation Concentration
CMC
SDS
70
Surface tension
Surface tension (mJ/m )
-2

60 Solubilty
50
Turbidity

40

30
1 10 100 1000
Concentration (mM)
What happen near cmc?

see Excel sheet

 Micelles
Hydrocarbon chains inside,polar head
groups outside
Spherical object of typically 30100
surfactant molecules,oily phase inside
(polydisperse)
Typical diameters 36 nm.
Interiors show liquid phase properties
Micelles are dynamic structures.
Exchange at s timescale.
 Temperature Dependence
Ionic surfactants
weak dependence
at low T, precipitation as crystals
Krafft temperature: solubility = CMC
consequence: low efficiency below Krafft
point
Temperature Dependence
Example:
SDS
 Temperature Dependence
Nonionic surfactants
at high T, formation of separate phase
cloud point

Pluronic
 Thermodynamics of Micelles
Entropy: bringing hydrocarbon tails out of
the water (hydrophobic effect) -> decrease
of CMC with increasing tail length
Lateral repulsion of headgroups: hydration
force, steric effects
Electrostatic repulsion for charged
surfactants -> influence of salt
concentration
Influence of chain length and salt
concentration on the CMC
Example:
alcylsulfate
in NaCl at
21C
Structure of Surfactants in Solution

Micelles
Cylinders
Bilayers

Determined by the
surfactant parameter
(packing ratio)
 Surfactant Parameter

VC AC
NS =
LC A0 A0
VC = Volume of the hydrocarbon tail
LC = Length of hydrocarbon tail
A0 = Area per head group
 Surfactant Parameter

VC AC
NS =
LC A0 A0
small values: high curvature
values ~ 1: small curvature
high values: inverse micelles
 Surfactant Parameter
LC LC LC

A0 A0 A0

NS = 0.33 NS = 0.5 NS = 1

Micelles Cylinders Bilayers

Structures of Surfactants
Micelle
Inverted
Micelles

Cylinder
or rod-like
aggregate

Bilayer
Vesicle
or
liposome
 Calculation NS
VC (nC 0.027 + 0.029 )nm 3

LC (nC 0.127 + 0.15 )nm

0.215

0.21

AC
0.205

0.2
0 5 10 15 20

n
 Example

SDS: A0 = 0.62 nm2

NS =
VC
=
(11 0.027 + 0.056 )nm 3
= 0.37
LC A0 (11 0.127 + 0.15)nm 0.62nm 2
Biological Membranes
 Functions of biological membrane
Effective barrier for ionic transfer and charges
Eq. 12.8:
compare dissociation energy in both media
e2 e2
diss
Eoil Ewater
diss
= = 33 kT
8 0 water 8 0 oil

Receptor proteins may be triggered to open

barrier
Bicontinuous structures
Emulsions
 Emulsions

Dispersion of two immiscible liquid phases

 Emulsions

Oil-in-water
Water-in-oil

in this context, oil may denote any liquid not miscible with water!
 Volume fraction d
Determines many properties, e.g.
Viscosity
Conductivity
 Polydispersity

1 (ln R ln R ) 2
P= exp
R 2 2 R
2

Lognormal distribution
 Types of emulsions
Macroemulsions
Only kinetically stable -> demulsification
0.5-10 m size of droplets
external driving force

Microemulsions
Thermodynamically stable
very small droplet size (nm)
equilibrium as driving force
 Formation of Macroemulsions
3V
Gem =
R
Energy required depends on surface
tension between liquids -> surfactants
In practice higher energies are necessary

0.40.6
R W
oil-in-water or water-in-oil?
oil-in-water or water-in-oil?
Volume fraction has little influence!

Dependence mainly on NS
for NS < 1, mainly oil in water
for NS > 1, mainly water in oil

On stirring, W/O and O/W both are formed

Criterion: which has lowest stability, disappears
 Aging of emulsions
Flocculation
Creaming
Coalescence
Phase separation
 Stabilization of Emulsions
Emulsifiers usually surfactants
Hydration force for oil-in-water
Steric force for water-in-oil
Electrostatic forces for charged surfactants
Polymers steric force
Powders hydrophobic force
 Microemulsions
Thermodynamic equilibrium
Spontaneous formation
react on external changes
droplet size 5-100 nm
form for high surfactant concentrations
(complete coverage of interphase)
driving force is the spontaneous curvature
of the surfactants
Estimation of drop size

4
V d = NR 3

3
V S = 4LS NR 2

3LS d
R=
S
Phase behavior of Microemulsions

Ionic surfactants: salt concentration

(changes headgroup area)

Nonionic surfactants: temperature

(changes hydration and fluctuations)
-> Phase Inversion Temperature
 Phase diagram: Example

Water / octane
microemulsion
with alkylethyleneoxide
more surfactant: (C12E5)
easier to contain PIT = 32C
all oil in droplets

curvature too
large to contain all
oil in droplets
 Phase transition
When T , then
size of head group (less hydration)
tail widens (thermal fluctuations)

Result: phase inversion through lamellar phase

 Conclusion
No foams
Surfactants form all kind of aggregates
controlled by relative size of components
Macro-emulsions very important for practice
Micro-emulsions:
specialty
modern research area